ELECTROCHEMISTRY AND SPECTROSCOPY OF INTRAMOLECULAR CHARGE-TRANSFER COMPLEXES - PARA-N,N-DIALKYLAMINOBENZYLIDENEMALONONITRILES
ELECTROCHEMISTRY AND SPECTROSCOPY OF INTRAMOLECULAR CHARGE-TRANSFER COMPLEXES - PARA-N,N-DIALKYLAMINOBENZYLIDENEMALONONITRILES
复制标题
DOI：
10.1021/j100458a027
复制
发表时间：
1980-01-01
影响因子：
--
通讯作者：
LAW, KY
中科院分区：
文献类型：
--
作者：
LOUTFY, RO;LAW, KY
本文研究了一系列对-N，N，N-二烷基氨基苯亚甲基丙二腈衍生物（1，2和3）的光谱和电化学性质。这些材料表现出很强的分子内电荷转移吸收。在该系列中，给电子基团（R2 N）的构象自由度通过烷基链将氮原子在结构上锚定到芳环上而逐渐受到限制。NR 2基团的分子旋转限制对非辐射衰变速率和激发态偶极矩有着深远的影响。但对基态偶极矩影响不大。当NR 2基团自由旋转时，观察到电子激发时偶极矩（µ）的最显著变化。二烷基氨基的内旋转速率估计为2 X 10 ns '1。
The spectroscopic and electrochemical properties of a series of p-iV^ ZV-dialkylaminobenzylidenemalononitriles derivatives (1, 2, and 3) have been studies. These materials exhibit a strong intramolecular charge-transfer absorption. In this series the conformational freedom of the electron-donating group (R2N) was progressively restricted by structurally anchoring the nitrogen atom to the aromatic ring by alkyl chains. Molecularrestriction of rotation of the NR2 group had a profound effect on the nonradiative decay rate and the excited state dipole moment. However, it had little effect on the ground state dipole moment. The most pronounced change in dipole moment (µ) on electronic excitation was observed when the NR2 group was free to rotate. The rate of internal rotation of the dialkylamino group was estimated to be 2 X 10n s'1.